The Radiolysis of Ethyl Mercaptan<sup>1</sup>

Myron, J. J. J.; Johnsen, Russell H.

doi:10.1021/j100881a039

Cited by 8 publications

(4 citation statements)

References 6 publications

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“…RSH + e---> RS + H (24) do not occur; these liquid systems are considerably less polar than water and the evidence is that reactions 23 and 24 become exothermic only if solvation energies in a polar medium can be utilized in the overall ener- However, simple dissociative attachment of e" need not necessarily be involved in steps 18 and 18a. An alternate explanation is that e~is captured by the sulfhydryl group to give RSH~and that chemistry then ensues as a consequence of proton transfer from an adjacent NH3+ group.26 Some evidence for such concerted action is to be found in the fact that (7(H2) + G?…”

mentioning

confidence: 99%

Radiation chemistry of the .alpha.-amino acids. .gamma. Radiolysis of solid cysteine

Peterson¹,

Holian²,

Garrison³

1969

J. Phys. Chem.

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mentioning

confidence: 99%

Radiation chemistry of the .alpha.-amino acids. .gamma. Radiolysis of solid cysteine

Peterson¹,

Holian²,

Garrison³

1969

J. Phys. Chem.

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“…However, radiolysis of pure ethyl mercaptan produced diethyl sulfide in 15% yield. 63 Thus, such an attack is a reasonable surmise for the appearance of a dialkyl sulfide radio-product (see below for details).…”

Section: The Journal Of Chemical Physicsmentioning

confidence: 99%

“…In the radiolysis of pure ethyl mercaptan, the carbon radical reaction at sulfur produced diethyl sulfide. 63 The small fractions of oxygenated products are unlikely to have arisen from the reaction with molecular oxygen because the sample was measured as a mineral oil mull spread on tape in a…”

Section: A Solid L-cysteinementioning

confidence: 99%

Synchrotron X-radiolysis of l-cysteine at the sulfur K-edge: Sulfurous products, experimental surprises, and dioxygen as an oxidoreductant

Frank

Sarangi

Hedman

2019

The Journal of Chemical Physics

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In situ inventory of sulfurous products from the sulfur K-edge synchrotron X-radiolysis of L-cysteine in solid-phase and anaerobic (pH 5) and air-saturated (pH 5, 7, and 9) solutions without and with 40% glycerol is reported. Sequential K-edge X-ray Absorption Spectroscopic (XAS) spectra were acquired. L-cysteine degraded systematically in the X-ray beam. Radiolytic products were inventoried by fits using the XAS spectra of sulfur model compounds. Solid L-cysteine declined to 92% fraction after a single K-edge XAS scan. After six scans, 60% remained, accompanied by 14% cystine, 16% thioether, 5.4% elemental sulfur, and smaller fractions of more highly oxidized products. In air-saturated pH 5 solution, 73% of L-cysteine remained after ten scans, with 2% cystine and 19% elemental sulfur. Oxidation increased with 40% glycerol, yielding 67%, 5%, and 23% fractions, respectively, after ten scans. Higher pH solutions exhibited less radiolytic chemistry. All the reactivity followed first-order kinetics. The anaerobic experiment displayed two reaction phases, with sharp changes in kinetics and radiolytic chemistry. Unexpectedly, the radiolytic oxidation of L-cysteine was increased in anaerobic solution. After ten scans, only 60% of the L-cysteine remained, along with 17% cystine, 22% elemental sulfur, and traces of more highly oxidized products. A new aerobic reaction cycle is hypothesized, wherein dissolved dioxygen captures radiolytic H • or e − aq , enters HO 2 • /O 2 •− , reductively quenches cysteine thiyl radicals, and cycles back to O 2 . This cycle is suggested to suppress the radiolytic production of cystine in aerobic solution.

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“…The results of the y-radiolysis experiments are not as clear cut as those for the photolysis, but since many of the products expected or purported to be formed (13,14,34) in y-radiolysis are the same as those found in the photolysis experiment, one can proceed with a certain amount of confidence using the knowledge of the properties of those radicals which are common to both systems and which have been prepared in similar molecular environments. The effects of y-irradiation on glasses such as 3MP have recently been reviewed (2).…”

Section: B Radiolysismentioning

confidence: 99%

The Photolysis and Radiolysis of Simple Mercaptans in Dilute Glassy Matrices

Skelton¹,

Adam²

1971

Can. J. Chem.

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The e.p.r. spectrum of thiyl radicals is obtained when dilute solutions of aliphatic mercaptans are photolyzed in a xenon matrix at 77 OK. No proton hyperfine structure is observed at low concentrations of thiol but it appears at higher concentrations due to the reaction of hot hydrogen atoms with solute mercaptan molecules. When small amounts of the thiols are dissolved in glassy hydrocarbon matrices such as 3-methylpentane, there is produced after photolysis hyperfine structure characteristic of the solvent as well as the thiyl resonance. The e.s.r. absorption due to the solvent species disappears when the matrix is warmed a few degrees above 77 "K but thiyl radicals are stable up to the melting point of the glass. The corresponding y-irradiated glasses do not give thiyl absorption, but two other species are produced along with solvent radicals. No thiyl radicals are observed following radiolysis, or upon photobleaching the new species. The spatial distribution of the neutral radicals in the glasses is discussed in view of these results.Le spectre de r.p.e. de radicaux thiyl est obtenu lors de la photolyse de solutions dilukes de mercaptans aliphatiques dans une matrice de xenon a 77 OK. On n'observe pas la structure hyperfine du proton en utilisant de faibles concentrations de thiol, mais elle apparait lorsqu'on utilise des concentrations plus ClevCes a cause de la reaction des atomes d'hydrogkne chauds avec les molCcules de mercaptan en solution. Si on dissout de petites quantites de thiol dans des matrices d'hydrocarbure vitreuses, tel le methylpentane-3, il se produit apres photolyse, une structure hyperfine qui est caracteristique du solvant aussi bien que de la resonance du thiyl. L'absorption r.p.e. due a l'espece solvant disparait quand la matrice est chauffee a quelques degris au-dessus de 77 OK, mais les radicaux thiyl demeurent stables jusqu'au point de fusion du verre. Les verres irradits aux rayons-y ne donnent pas d'absorption thiyl, mais deux autres especes sont produites en meme temps que les radicaux de solvant. On n'observe pas de radicaux thiyl apres radiolyse, ou pendant la photodCcoloration des nouvelles espkces. On discute de la distribution spatiale des radicaux neutres dans les verres pour arriver aces rksultats.

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The Radiolysis of Ethyl Mercaptan¹

Cited by 8 publications

References 6 publications

Radiation chemistry of the .alpha.-amino acids. .gamma. Radiolysis of solid cysteine

Radiation chemistry of the .alpha.-amino acids. .gamma. Radiolysis of solid cysteine

Synchrotron X-radiolysis of l-cysteine at the sulfur K-edge: Sulfurous products, experimental surprises, and dioxygen as an oxidoreductant

The Photolysis and Radiolysis of Simple Mercaptans in Dilute Glassy Matrices

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The Radiolysis of Ethyl Mercaptan1

Cited by 8 publications

References 6 publications

Radiation chemistry of the .alpha.-amino acids. .gamma. Radiolysis of solid cysteine

Radiation chemistry of the .alpha.-amino acids. .gamma. Radiolysis of solid cysteine

Synchrotron X-radiolysis of l-cysteine at the sulfur K-edge: Sulfurous products, experimental surprises, and dioxygen as an oxidoreductant

The Photolysis and Radiolysis of Simple Mercaptans in Dilute Glassy Matrices

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The Radiolysis of Ethyl Mercaptan¹